DOI: 10.1063/1.1677406. Mechanism of Rotational Relaxation

10.1063/1.1677406

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

It has been known for some time from infrared chemiluminescence experiments that a nonthermal rotational distribution of hydrogen halide peaked initially at high rotational quantum number, J, relaxes to a thermal distribution without generating a peak at intermediate J [Discussions Faraday Soc. 44, 183 (1967)]. It is shown in the present study that this characteristic pattern of relaxation is well described by a model according to which ΔJ is unrestricted, except for the relation PJ−ΔJJ=N exp (— CΔE), where PJ−ΔJJ is the probability of a collision−induced transfer from J to J — ΔJ, ΔE is the energy difference between these two rotational states, and N and C are constants. This expression for PJ−ΔJJ ascribes a very much lower probability of rotational deactivation to the higher J levels. Three other, contrasting, models were tested; they were rejected since they failed to describe the observed pattern of relaxation adequately. Upper limits were ascribed to PJ−ΔJJ for ΔJ=1–5 in HCl–H2 collisions. This study provides a further method for correcting infrared chemiluminescence data for modest rotational relaxation and at the same time shows that the simple truncation correction procedure used until now is remarkably good.

Bibliography

Polanyi, J. C., & Woodall, K. B. (1972). Mechanism of Rotational Relaxation. The Journal of Chemical Physics, 56(4), 1563â1572.

Authors 2

J. C. Polanyi (first)
K. B. Woodall (additional)

References 30 Referenced 345

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{'key': '2024020908351541000_r1a'}
{'key': '2024020908351541000_r1b'}
10.1039/DF9623300107 / Discussions Faraday Soc. (1962)
10.1063/1.1695750 / J. Chem. Phys. (1965)
10.1063/1.1733452 / J. Chem. Phys. (1963)
10.1063/1.1673175 / J. Chem. Phys. (1970)
10.1063/1.1726197 / J. Chem. Phys. (1964)
10.1063/1.1670508 / J. Chem. Phys. (1968)
10.1039/tf9696501177 / Trans. Faraday Soc. (1969)
10.1063/1.1726902 / J. Chem. Phys. (1966)
10.1063/1.1840432 / J. Chem. Phys. (1967)
10.1038/2151267a0 / Nature (1967)
10.1039/DF9674400183 / Discussions Faraday Soc. (1967)
10.1063/1.1744487 / J. Chem. Phys. (1958)
10.1143/ptp/9.6.578 / Progr. Theoret. Phys. (Kyoto) (1953)
10.1063/1.1742849 / J. Chem. Phys. (1956)
10.1063/1.1743326 / J. Chem. Phys. (1957)
10.1063/1.1672004 / J. Chem. Phys. (1969)
10.1063/1.1672005 / J. Chem. Phys. (1969)
10.1063/1.1673882 / J. Chem. Phys. (1970)
10.1364/AO.10.001738 / J. Appl. Opt. (1971)
{'key': '2024020908351541000_r20'}
10.1021/ar50016a002 / Acc. Chem. Res. (1969)
10.1063/1.1670019 / J. Chem. Phys. (1968)
{'key': '2024020908351541000_r23'}
10.1016/0009-2614(71)80636-X / Chem. Phys. Letters (1971)
{'key': '2024020908351541000_r25'}
10.1063/1.1701220 / J. Chem. Phys. (1961)
10.1039/df9623300044 / Discussions Faraday Soc. (1962)

Dates

Type	When
Created	21 years, 6 months ago (Feb. 6, 2004, 3:25 p.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 4:28 a.m.)
Indexed	3 months, 2 weeks ago (May 5, 2025, 9:54 p.m.)
Issued	53 years, 6 months ago (Feb. 15, 1972)
Published	53 years, 6 months ago (Feb. 15, 1972)
Published Print	53 years, 6 months ago (Feb. 15, 1972)

Funders 0

None

BibTeX

@article{Polanyi_1972, title={Mechanism of Rotational Relaxation}, volume={56}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1677406}, DOI={10.1063/1.1677406}, number={4}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Polanyi, J. C. and Woodall, K. B.}, year={1972}, month=feb, pages={1563–1572} }

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